Solvent refining oil



Aug. 23, 1938.

RAFFINATE On. -u-

W. B. HENDR EY SOLVENT REFINIHG OIL Fld OGL 17, 1936 RAFFINATE PHASE l-l ExTnAcT PHASE wALocnsc; B. HENDREY INVENTOR ATTORNEY Patented Aug. 23, 193s UNITED STATES PATENT oFFicE SOLVENT BE'FINING OIL Application October 17, 1936, Serial No. 106,097

2 Claims.

This invention relates to a process for solvent reiini'ng of hydrocarbon oil, and more particularly to a process for refining petroleum and fractions derived therefrom.

The invention contemplates refining oil with a selective solvent of the phenol type, such as phenol, chlorphenol, etc. It contemplates a method in which the solvent is recovered from the oil subsequent to the reiining operation by treating the mixture of oil and solvent with ammonia, preferably anhydrous ammonia. under conditions of temperature and pressure such that the selective solvent compound of the phenol type forms with the ammonia an addition compound which is substantially immiscible with the oil. The addition compound can then be readily separated from the oil by decantation or other means. In this way, the phenol type of solvent is separated from the oil and is subsequently recovered for reuse upon decomposition of the addition compound.

Selective solvents, such as phenol andohlorphenol, when mixed with anhydrous liquid ammonia. in substantially equal molecular proportions, form compounds which are stable under elevated pressure, and which decompose with reversion to the original compounds when the pressure is released. Flor example, phenol reacts with liquid ammonia under pressure to form ammonium phenolate, a compound which breaks down readily when the pressure is released, liberating ammonia for reuse in the process. Chlorphenols also form the corresponding ammonium chlorphenolates, and these compounds likewise vbreak down upon reduction oi the pressure liberating am nia.

Accordiirgygany invention ves the applica.- tion of the va'bve principle tof solvent refining of hydrocarbon oils. such asmineral oils, as a means of recovering selective solvents of the phenol type from the oil undergoing treatment. This method o i'-,.recovery-is advantageously applied where tlel oil undergoing treatment'is a gasoline or naphtha fraction, and in which case 4the boiling point of vthesolvent may be .l'thin the lling range of the gasoline fraction undergoing I, tm'ent, so that it is dimcult, if not impossible, t'o 'separate the solvent from the gasoline by the conventional distillation method. 45C It is, of course, contemplated that the invention is applicable to the treatment of other types ot oils. such as lubricating oil fractions.

- In practicing the invention, the ou te be treated is mixed with a selective solvent, such as phenol. under conditions such that the oil and solvent (Cl. ISG-13) mixture separates into extract and raffinate phases. The extract phase comprises the bulk of the solvent with the soluble constituents of the, oil dissolved therein. The raiiinate phase comprises the insoluble portion of the oil together with a relatively small amount 4o!! the solvent liquid.

Thus, in the usual solvent refining operation, as applied to the treatment of lubricating oil stock, the extract phase comprises the low viscosity index constituents dissolved in the solvent, while the raffinate phase comprises the high viscosity index and relatively paraiiinic constituents of the oil mixed with a small amount oi the solvent.

These two phases are separated and. in accordance with the method of my invention. are separately treated with liqueiled anhydrous ammonia under the proper conditions of temperature and pressure. The phenol combines with the ammonia to form an addition compound, as already explained, which is stable only under pressure, and which is substantially. immiscible with the oil but soluble in any excess ammonia that is present. Upon standing, under pressure, the addition oompound separates from the oil, leaving it substantially free from the solvent.

The separated portion, comprising the addition compound and excess ammonia, is then withdrawn and conducted to a vessel wherein the pressure is released so that the compound decomposes with the liberation of ammonia, and the consequent recovery of the solvent in its original form.

In order to illustrate the invention, as applied to the solvent reilning of mineral oil; reference will now be made to the accompanying flow diagram.

The oil to be treated is drawn from a source not shown and introduced to the lower portion 40 of an 'extractiontower l, while the solvent, phenol, is also conducted from a source not shown, and introduced to the upper portion of the tower.

The temperature maintained within the tower will-depend upon the degree of extraction desired as ivell as the nature ot the oil undergoing treatbut generally will be around about to F. The solvent is introduced to the tower in the ratioof about two to tour parts o! the solvent to one part oi' oil.

The extraction tower is advantageously of the conventional packed type adapted to effect countercurrent contact between the oil and the solvent. T

The raffinate phase accumulates in the upper u 2 l 'valasip'aa portion of the tower. while theextract phase accumulates in the le er portie-n thereof. The raiilnate phase is continuously removed 4 and conducted by a pump to' a mixer Z maintained under pressure and wherein it is mixed with liquid ammonia drawn from a'tanl: Bf The pressure required the mmer 2 will depend upon the prevailing temperature, Where the temperatures range from 50 to 120 F., for example.

the pressure required will range from' 90 to about The ammonia thus reacts .with'the phenol. I contained in the remnate phase to form the The pressure is released to substantially atmospheric pressure in the separator- 5 'soth'at-` `decomposition ot the phenolate with liber'- ation of the ammonia in gaseous form. The

-phenol is drawn o'irom .thebottom of tiiejseparater as indicated. andis available for reuse'. l f

Vaporization of the'amnionia within the separator 5 causes a refrlgerative effect and this may he utilised for cooling the liberated ammonia. either-before or after compression.' This may be accomplished by conducting the ammonia through a coil located within the separator l. as' indicated, The compressed and cooled ammonia islthenreturned in liquid 'form to the storage tank 3 for reuse.

'The extract phase from-the bottom of the extraction tower I is also conducted to a separate mixer 6, as indicated. and wherein it'is also mixed with liquid ammonia from the storage tank 3.' From the mixer 6, the liquid mixture is conducted to a separator l. similar to the separator 4 already described, and wherein the extract oil is separated from the ammonium phenolate. Extract oil is removed as indicated, while the ammonium phenolate and excess ammonia is conducted to a separator 8. similar to the separatpr 5 previously described. and wherein the While I have 'referred to -my invention. as

applied to solvent reilning operations in which phenol and chlor-phenol'are employed as the selective solvents, it is contemplated that a modlilcation of the invention may be made where other typeso! selective solvents are used. such as nitrobenzenaaniline. benzyl alcohol, benzyl amine, phenyl cyanideg etc. While .the ammonla may not form reaction compounds with` these" particular solvents, nevertheless it may he as awashlng solvent with which to wash or extract the solvents 1in question from mineral oil, The solubility. ot mineral` oil in liquid ammonia is very small, whereas solventsotthe type mentioned-above are highly soluble or completely mlsclble with liquid ammonia'. Consequently, hy

- separately washing the extract and raffinate phases with liquid ammonia, it is possible to dispace the 'selective solvents in question from the 0 'This washing treatment is advantageously carried out' under pressure.l The solution o selectlve'solvent in ammonia is withdrawn and conducted -to aj'se'parate vessel. -whereinthe pressureisreleasedand the ammonia separated from the selective solvent by vaporization.4 ""'Oluviouslyl many 'modifications and variations .oi the invention, as herelnbefore set iorth.`may be made-'withoutdepartingufmm the 'spirit m scope' thereof; and therefore only such limitations should 'be imposed 'asiare indicated in the ap.

molecular proportion with the phenol and under a pressure suiiiciently elevated above atmospheric so that substantially all the phenol-ls converted into an addition compound substantially immiscible with the oil, separating the addition compound formed from theV mixture while under said elevate'dpressure, introducing the withdrawn compound to a zone of reduced pressure such that the compound is decomposed into ammonia and the original phenol solvent without application of heat, and removing the product so formed.

2. The method according to claim 1 in which the ammonia and oil containing phenol solvent are mixed under a pressure of to 300 pounds whlleat a temperature of 5U to120 F.

' l WAIDERSEE B. HENDREY. 

